Process of texturizing dyed thermoplastic yarns



Aug. 9, 1966 E. PICKUP ETAL raoczss or mxwuaizme 'mm'n wamnuorms'nc mans Filedlov. 21. 1964 2 Shoetw-Shoat 1 EDMUND PICKUP JOHN E. CL A R K ATTORNEYS Aug. 9, 1966 E. PICKUP ETAL A PROCESS Ol' TEXTURIZING DYED THERMOPLASTIC YAR NS Fuod Nov. 27 1964 -2 Shasta-Sheet a INV EDMUND "PICKUP JO BY "N E CLARK United States Patent Office 3,264,815 PROCESS OF TEXTURIZING DYED THERMO- PLASTIC YARNS Edmund Pickup and John E. Clark, Charlotte, N.C., as-

sig'nors to Standard Chemical Products, Inc., Hoboken, NJ., a corporation of New Jersey Filed Nov. 27, 1964, Ser. No. 415,860

11 Claims. (Cl. 57-157) This application is a continuation-impart of our copending application Ser. No. 266,924, filed Mar. 21, 1963, and now abandoned.

This invention relates to a process of texturizing dyed thermoplastic yarns. More particularly, this invention relates to a process of texturizing dyed thermoplastic yarns utilizing a false-twist apparatus where in the dyed thermoplastic yarn is subject to temperatures in excess of 400 F.

In the process of preparing stretch or texturized yarn, the yarn, which may be a thermoplastic yarn or a nonthermoplastic yarn impregnated with a thermoplastic resin, is twisted to a variable degree, subject to a sulficient amount of heat usually in excess of 400 F. to substantially render the thermoplastic constituency of the yarn in a plastic condition, cooled to set the yarn, and thereafter untwisted. This process, well known in the art, may be done by batch methods or by the so-called false-twist method, wherein the yarn is run through an apparatus which simultaneously twists, heat-sets and untwists the yarn. In the processing of the yarn through the so-called false-twist apparatus, the heat is applied by passing the yarn through a heater. This heater can be either a direct heater in which .the yarn is in direct contact with the metallic surface of the heater or it can be an indirect induction heater. Yarn passing through the continuous method machines is ordinarily utilized in the undyed state and, thereafter, the bulked yarn is dyed in the form of muffs in package dyeing machines. Such a method suffers the drawback that the yarn loses a considerable amount of its bulk and often as high as 25% of its stretchin the future dyeing operation. It is, therefore, of considerable advantage to be able .to dye the yarn before processing through the so-called false-twist continuous apparatus, as provided for in this invention.

In the United States Patent No. 2,803,109 a method is described for dyeing yarn by passing the same through a dye bath prior to its passage through an induction heater and the false-twist spindle. This method is not satisfactory when performed on apparatus wherein the yarn is bulked by indirect heating because of friction drag and breakage of the wet yarn and cannot be used at all in apparatus wherein the yarn comes into direct contact with the metallic surface of the heater. Moreover, the use of such apparatus as described in US. Patent No. 2,803,109 suffers the drawback in that the speed of the yarn running through the machine must be sufficiently slow in order that the same can be heated properly throughout its cross-sectional area. come in the prior art by passing the yarn over the metal surfaces of a heater in direct contact with the heater. In such processes. the speed of the yarn through the heater area and the false-twist" spindle area can be materially increased. However, it has been impossible to process dyed yarns through such false-twisting apparatus when the dyed yarn comes into direct contact with the heater element. Bulked yarns produced by this improved process have theretofore been dyed subsequent to the bulking operation with a considerable loss in the stretch of the bulked yarn.

In the United States Patent No. 3,077,724 a method is described for bulking yarn by feeding the yarn through a static eliminator or a liquid-applicator device" before This drawback has been overi passing the same through the indirect or radiant heater 0 and false-twist spindle and it is indicated that it is desirable to eliminate static fromthe yarn to prevent the yarn from contacting the central tube of the heater so that the heat applied to the yarn is freely radiant. It is indicated that plain water acts as a static eliminator. However, elimination of static from the yarn or wetting the same before its passage through the false-twist" continuous apparatus does not prevent static accumulation on the yarn during the processing of the yarn through the apparatus. As soon as the yarn becomes dry, it must be both dry and heated to a minimum temperature of about 400 F. before it will take a permanent set in the falsetw'ist" machine, static will be produced. The elimination of static from the yarn prior to its passage through the radiant heaters either by wetting the same or passage through a static eliminator will not avoid the build-up of static electricity due to the very rapid passage of the yarn through heaters wherein it is heated toa high degree of temperature.

It is an object of the present invention to develop a process of texturizing dyed yarn, which dyed yarn is continuously texturized in conventional false-twist" apparatus, both where the dyed yarn passes through a heated zone and where it comes into direct contact with the heating element.

It is a further object of the invention to apply an antistatic agent to dyed yarns prior to processing them through false-twist apparatus.

It is a still further object of the invention to effect the dyeing of yarn by passing the yarn through a dye bath containing an antistatic agent prior to its passage through a false-twist apparatus, applying heat, preferably by direct contact with the yarn whereby the dye is set by passage through the heating zone in direct contact with the heater.

Another object of the. invention is 'to apply a high temperature lubricant and antistatic agent to the dyed yarn or to the dye bath through which the yarn passes prior to its processing through a false-twist apparatus wherein the thermoplastic yarn is heated to temperatures in excess of 400 F.

These and other objects of the invention will become more apparent as the description thereof proceeds.

We have now discovered that dyed yarn may be texturized in a false-twist" apparatus if this dyed yarn contains therein an antistatic and lubricatingagent, preferably a permanent antistatic agent, which likewise is set by heat. A further improvement in this process is to utilize the same in a one-step operation wherein the yarn is passed through the conventional false-twist" apparatus by passing the yarn through a dye bath containing the appropriate dyes and adjuvants and an antistatic agent, prior to passing the same to the heating zone of the false-twist apparatus.

As a still further improvement, we have now discovered that dyed yarn may be texturized in a false-twist" apparatus without excessive smoking when heated to a temperature in excess of 400 F. if this dyed yarn contains thereon a high temperature lubricating and antistatic agent. A further improvement in this process is to utilize the same in a one-step operation wherein the yarn is dyed before passage through the conventional false-twist? apparatus by passing the yarn through a dye bath containing the appropriate dyes and adjuvants and a high temperature lubricant and antistatic agent, prior to passing the same to the heating zone of the false-twist" apparatus where the yarn is heated in excess of 400 F.

While we are not sure of the mechanism involved in the practice of our invention, we believe that conventional dyed yarns, when passed through the false-twist apparatus, especially in direct contact with the heater, generate Patented August 9, 1966 sufficient electrostatic charges as to create such a frictional drag that the yarn cannot be processed at the speeds involved. For some reason not known to us, this effect is not had in undyed yarns.

Moreover, this same effect is true whether a previously dyed yarn is processed or whether the undyed yarn is passed through a dyebath and then through the heating zone of a false-twist apparatus while still moist.

In the figures:

FIG. 1 shows a schema-tic outline of the yarn feed through a commercial stretch yarn or texturizing machine utilizing the process of the invention;

FIG. 2 shows the yarn feed through another commercial type of stretch yarn or texturizing machine utilizing the process of the invention;

FIG. 3 shows the yarn feed through another commercial type of stretch yarn or texturizing machine utilizing the process of the invention.

There are several false-twist" machines on the market both wherein the yarn is passed through an indirect heating zone and wherein the yarn is passed in direct contact with the metal surface of the heater before passing through the false-twist" spindle. Any one of these can be utilized in the practice of our invention, especially when modified slightly in order to pass the yarn through a dye bath prior to texturizin-g. Among the modifications of the invention, FIG. 1 represents the string-up diagram of one such stretch line machine sold under the name Superloft. The yarn from :pirns 1 is drawn through guides 2a, 2b and 20, combined through guide 3, and passes through tension disc 4. Thereafter, the yarn passes through guide, 5, guide 6 and around dye bath feed roll 25. The yarn is passed around dye bath feed roll 25 the requisite number of turns in order to obtain correct penetration of the dye at the speed of operation selected. Dye 'bath feed roll 25 is immersed in a dye bath liquid 24 contained in a dye bath trough 23. Thereafter, the yarn passes through heater 8 in direct contact with the metal heater surface 9. The heater is of sufficient length in order to heat the yarn passing through to the temperature desired, preferably about 400450 F. or higher. Thereafter, the yarn passes through thread line guide 10 and into the "false-twist spindle 11. This spindle is rotated at speeds up to 350,000 rpm. Above the false-twist spindle 1l1, the thread passes through twist trap wheel 12, guide 13, to the take-up packages. In FIG. 1, two takeup packages 16a and 16b are shown, with the yarn being divided between the two, half of the yarn passing to guide *15 to take up package 16a driven by package drive roll 14a, the other half of the yarn being passed through guide 17bto take-up package 16b, driven by package through roll '14 In FIG. 2, the string-up diagram of another commercial false-twist machine, the Whitin-A.R.C.T., is shown. In this embodiment, a series of pirns 1 containing the yarn supply are passed through guides 2a, 2b, 2c, 2d, 22 and 2}, combined and passed through guide 3 and onto dye bath feed roll 25. Dye bath feed roll 25 is immersed in a dye bath 24 contained in dye bath trough 23. On leaving the dye bath, the yarn passes through guide a, tension disc 4, guide 5b, and feed rolls 6 into the heater stage. In the particular embodiment, two heat stages are shown. For most stretch woven fabrics, the stretch yarn is produced using the first processs'tage only, with the second heat zone inoperative. However, for larger diameter yarn, both heaters are required. The yarn passes through heater 8a in contact with the metal heater surface 9a, and through the false-twist" spindle assembly 11. Thereafter, if desired, it can be passed through guide 50, second feed roll 7, heater 8b, in contact with the metal heater surface 9b. The yarn from either the first or the second heat stage is next passed through guide 18 and tensioning device 19, and thereafter through guides 20a, 20b, and 22 to the various take-up packages. In the particular embodiment, three take-up packages 14a, 14b and 14c are shown. The yarn is split into thirds and passed through guides 22a, 22b and 220, onto the take-up packages 14a, 14b and 14c. The take-up packages are driven by package drive rolls 16a, 16b and 16c.

In FIG. 3, the string-up diagram of the commercial false-twist" machine described in U.S. Patent No. 2,803,- 109, is shown. In this embodiment, a pirn 1 contains the yarn supply. The yarn is drawn from the pirn 1 through guides 2 and 3 and onto dye bath feed roll 25. Dye bath rfeed roll 25 is immersed in a dye bath 24 contained in dye bath trough 23. On leaving the dye bath, the yarn passes through guides 5a and Sb and tensioning device 4 into the heater stage. The yarn passes through heater 8 which is heated electrically. The yarn passes through the heated zone but does not directly contact the heated sides of the heated zone. Thereafter the yarn passes through guide 50 and through the false-twist" spindle assembly 11. The twisted yarn is then passed through spaced rolls 26 and 27, guide 20, traverse guide 28 onto take-up package 16. The take-up package 16 is driven by package drive roll 14.

Our invention can be applied to any of the yarns normally processed in the false-twist" apparatus for the production of texturized, bulked or stretch yarn. Ordinarily,

thermoplastic yarns such as nylon, Vinyon, Orlon, Velon,

, thermoplastic resins, such as cotton, linen, wool, etc., the

processing of which, through false-twist" apparatus, is described in U.S. Patent No. 3,025,659.

All customary dyes utilized to dye the above yarns may be employed and utilized with the various dye adjuvants, such as wetting agents, buffering agents, etc. Any antistatic agent may be employed in the process by adding the same to the yarn either separately if the yarn has been previously dyed or incorporated with the dye bath. It is preferable to incorporate from 0.1% to 8% of the antistatic agent based on the weight of the yarn, and for good antistatic finishes especially with polyamide fibers from 0.3% to 5% should be applied. The yarn, after processing, should contain from about 0.1% to about 8% of the antistatic agent based on the weight of the dyed texturized yarn. An antistatic agent should be employed which is compatible with the dye bath if utilized in connection with the dye bath and at concentrations of from about 2% to about 20%. It is preferable to utilize a permanent type of antistatic agent which will set on the fiber and remain thereon after subsequent processing or to utilize a hightemperature-stable antistatic agent. The use of either of such materials is found to be helpful not only in processing the yarns through the false-twist apparatus but in subsequent processing, such as knitting, weaving, etc.

The so-called permanent antistatic agents are those which are water-soluble resinous preparations which undergo hardening upon heating or aging. Preferable among these are hardenable condensation products containing residual epoxide and halogen groups, such as are produced by condensing a vicinal epoxide-mono-halo-lower 'alkane, such as epichlorohydrin, with a polyoxylatepolyamine as described in British Patent No. 880,898.

The antistatic agents of a non-permanent type include all those which are suflicicntly low in volatility to remain on the yarn after passage through the heaters of the falsetwist apparatus to an extent of from 0.1% to about 8% based on the weight of the yarn. Among these antistatic agents can be mentioned:

(A) Mineral oils.-Those oils derived from petroleum stock, usually highly refined products free from unsatunated compounds and possessing a high degree of chemical stability.

(B) Triglycerides of higher fatty acids.-Representcd by natural occurring materials such as peanut oil, castor oil and tallow, or man made products such as glycerol triolein.

' v (C) Sulfated triglycerides of higher fatty acids-Prod- .ucts derived from the sulfation of triglycerides listed un- I gas are employed.

(D) Partially saponified triglycerides of higher fatty acids-Derived by partially saponifying the products mentioned under B with caustic soda or caustic potash in the presence of glycols.

(E) Sulfated higher fatty acids.-Products derived by sulfating oleic acid, coconut fatty acids, and tall oil fatty acids using the sulfating agents mentioned in C.

(F) Higher fatty acid esters with alkanols.--Reaction products of saturated and unsaturated higher fatty acids and alcohols, e.g. those that have from about 8-22 carbon atoms in the acid moiety and from 1-22 carbon atoms in the alcohol moiety, among which may be mentioned the following: methyl stearate, ethyl stearate, propyl stearate, isopropyl stearate, butyl stearate, octyl stearate, decyl stearate, dodecyl stearate, tridecyl stearate, hexadecyl steanate, eicosyl stearate, etc. High molecular weight esters of other fatty acids may also be used such as butyl caprylate, butyl capra-te, butyl laurate, butyl myristate, butyl palmitate, butyl behenate, octyl capyrylate, octyl capr-ate, octyl laurate, octyl myristaite, octyl palmitate, octyl palmitate, octyl behenate, decyl caprylate, decyl caprate, decyl laurate, decyl myristate, decyl palmitate, decy'l behenate, dodecyl caprylate, dodecy'l caprate, dodecyl laurate, dodecyl myristate, dodecyl palmitate, dodecyl behen-ate, tridecyl caprylate, tridecyl caprate, tridecyl laurate, tridecyl myristate, tridecyl palmitate, tridecyl behenate, 'hexadecyl caprylate, hexadecyl caprate, hexadecyl 'laurace, hexadecyl my-ristate, hexadecyl palmitate, hexadecyl behenate, eicosyl caprylate, eicosyl caprate, eicosyl laurate, eicosyl myristate, eicosyl palmitate, eicosyl behenate, and the like.

(G) Sulfated higher fatty acid esters with alkanols. Products derived from the sulfation of propyl oleate, isopropyl oleate, and butyl oleate using the sulfating agents mentioned in C. 1

(H) Sulfated esters of tall oil fatty acids with alkanols.--Products derived from propyl, isopropyl, and butyl esters of tall oil fiatty acids using the sulfating agents mentioned in C.

(I) Sulfated higher alkanoIs.- Products derived from the sulfation of alcohols ranging from C to C and mixtures thereof, examples of which are Alfol 6, Alfol 8, Alfol 10, Alfol 12, Alfo1*14, Alfol 16, Alfol 18, Alfol 20, Alfol 610, Alfol 810, Alfol 12-14, Alfol 1216, Alfol 1618C, and Alfol 16178, and Lorol 5, Lorol 7, Lorol 11, Lorol 22, and Lorol 28.

(J Ethoxylated higher aIkan0ls.-Represen ted by the alcohols ranging from C to C which have been ethoxylated with 1-20 moles of ethylene oxide, examples of which are Alfonic 1218-6, Alfonlc 1012-6, Alfonic 121'8-7, Allfonic 1218-8, the polyoxyethylene 6 ether of tridecyl alcohol (Glycosperse TBA-6), Poe 4 lauryl alcohol, and the like.

(K) Sulfated ethoxylated higher alkanols.-Reaction products of those alcohols listed under J using the sulfating agents mentioned in C.

(L) .Nonyl phenol ethaxylates.-Represented by Ter- I gitol Nonionic NPX, Tergitol Nonionic TP-9, Tergitol Noniom'c NP-33, Tergitol Nonionic N P-14, and Tergitol Nonionic N P-27.

(M) Higher fatty acid esters of gIyc0ls.-Reaction products of saturated and unsaturated higher fatty acids represented by those previously mentioned and the glycol moiety which can be represented by the following: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,5-pentanediol, hexylene glycol, 2-methyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, 1,2,6-hexanetriol, neopentyl glycol; also the higher molecular weight glycols for exam- 6 ple: polyethylene glycol 200, polyethylene glycol 300,

polyethylene glycol 400, polyethylene glycol 600, poly-' ethylene glycol 1000, polyethylene glycol 1500, polyethylene glycol 1540, polyethylene glycol 4000, polyethylene glycol 6000, polyethylene glycol 9000, and the like.

(N) Higher fatty acid esters of polyhydric compounds-Reaction products of saturated and unsaturated fatty acids represented by those previously mentioned and the polyhydric moiety which can be represented by materials such as trimethylolpropane, pentaerythritol, and the like.

. (0) Higher fatty acid esters of ethoxylated alcohols- Reaction products of saturated and unsaturated fatty acids represented by those previously mentioned and an ethoxylated alcohol represented also by those previously mentioned under I.

(P) Higher fatty acid amides.Reaction products of saturated and unsaturated higher fatty acids represented by those previously mentioned and with the amine moiety which can be represented by the following: alkanolamines, e.g. monoethanolamine, diethanolamine, triethanola-mine, N-methyl ethanolamine, N-ethyl diethanol-amine, monoi-sopropanol-amine, diisopropanolamine, t-riisopropanolamine, mixed isopropanolarnine; or the alkyl and alkylene amines for example; ethyl amine, diethyl amine, triethy-l amine, propyl amine, dipropyl amine, isopropyl amine, diisopropyl amine, butyl amine and the like, having up to 22 carbon atoms, or the alkyl and alkylene polyamines such as ethylene (ii-amine, diethylene triamine, triethylene tetramine, tetr-aethylene pentamine, propylene diamine, and the like.

(Q) Iml'damlines-Reaction products of saturated and unsaturated higher fatty acids represented by those previously mentioned, and an amine such as aminoethylethanolamine where a condensation is carried out to a cyclization of the compound.

(R) Sodium xyiene or toluene sulf0nates.-Products obtained by the sulfonation of xylene and toluene, and are usually used in formulations as coupling agents.

Among the above antistatic agents it is preferable to use compositions containing mineraloil, partially saponified triglycerides and sulfated fatty esters. Such prodnets are water-e mulsifiable and form stable emulsions in water. A typical composition is one containing from 50 to 75% mineral oil, 10 to 30% degraded triglycerides, 2 to 20% sulfated fatty esters, and, optionally, small amounts up to 10% potassium salts of higher fatty acids. As previously stated, it is especially preferable to utilize a high-temperature-stable antistatic agent in the process of the invention. These compositions are relatively more heat stable. This is accomplished by avoiding the use of sulfated products (often erroneously referred to as sulfonated), degraded triglycerides (soaps) and-low molecular weight esters described above. Most of the sulfatcd products today are derived by sulfating an unsaturated animal or vegetable oil with sulfuric acid, 66 B. H 98% H 80 oleum, etc. These sulfated materials are not heat stable and hydrolysis of the ester linkage (C'-0-SO OH) occurs at elevated temperatures. Low molecular weight esters such as butyl stearale are completely lost at elevated temperatures of 392 F.

These high-temperature-stable antistatic agents are particularly reaction products of alphasulfo higher fatty acids having the following linkage:

wherein the sulfur atom is directly attached to the carbon atom alpha to the carbonyl radical. The unsatisfied valences of the above compounds can be ester or amine radicals. Preferably among these compounds are an organic amine salt of an ester of an alphasulfo higher fat ty acid, wherein the alcohol moiety ofsaid ester is a member selected from the group consisting of glycols and ethoxyiated alcohols, as exemplified by the copending, commonly-assigned United States patent application Ser. No. 346,390, filed Feb. 21, 1964 and an Organic amine salt of an alphasulfo higher fatty acid, wherein the alcohol moiety of said ester is a higher fatty alcohol, as exemplified by the copcnding, commonly-assigned United States patent application Ser. No. 269,186, filed Mar. 29, 1963, and now abandoned. It is to be understood that the above-namcd alphasulfo higher fatty acid esters may also be employed in compositions containing esters of higher fatty acids.

It is preferable to utilize an antistatic agent having some lubricating property and all ofthe above-mentioned materials have such property.

The following examples are illustrative to the process of the invention. They are not, however, to be deemed limitative.

Example I A dye bath was prepared of the following composition:

Nylon yarn (70-34-V2Z) was dyed by passing the same through the dye'bath trough of a sizing machine using a roll speed of 8 r.-p.m. The yarn subsequent to passing through the dye bath was wound on a sizing tube. The yarn traveled through the dye bath at a speed of approximately 700 yards. per minute. The tubes of yarn were steamed in a Lydon box for 2% hours at 170-180 F., then dried in an oven for 30 minutes at 225 F. The dyed yarn was then processed through the Superloft false-twist" machine, converted to 2-ply in the operation. The yarn was processed at 440 F. over a 9 Superloft direct-contact heating block at 42 yards per minute. The resulting bulk yarn was knitted on a 200 needle, 3 /2 cylinder, 48 gauge machine.

The knitted yarn was found to have excellent color fastness to light (carbon-arc lamp) A.A.T.C.C. Test No. 16A-l960; fair to good color fastness to washing (No. 3 wash test) A.A.T.C.C. Test No. 39-1961; excellent color fastness to dry-cleaning (A.A.T.C.C. Test No. 85- 1960T); and excellent antistatic properties after five domestic launderings.

Nona-120+ indicates over 2 minutes.

ll'l designates hall-time." The sample oncineh wide is mounted at a stand touching the rollectrodc oi the Rothschild tntlc voltmeter. Vhon an auxiliary curront (supplied by the static voltmeter) is applied o the rollactro lc which is in contact with the sample, a reading is cgistcred on the dial oi the static voltmeter (about 80 volts). As soon LS the auxiliary current is removed from the rollcctrode, the reading of he dial would gradually drop back to zero. HT is the time in seconds eqnlred tor the reading to drop back to one-half of the initial reading. lhis is the resistance test oi the fabric.

'lim sample is then mounted vertical about 4 inch away from the roloctrodc iorthe following tests:

L =clliargtls in volts alter rubbing the sample five times with a stee ro' L =chargc in volts one minute alier termination of rubbing.

FllT=lluld dissipation, half-time. The time required for I." to full to A ot'lts initial value.

An ideal static free sample has zero F11 '1 readings in all cases.

The dyes utilized are conventional dispersed dyes used in dyeing nylon. Stanax is a modified water-soluble synthetic resin permanent antistatic agent in the form of a viscous liquid with approximately 50% solids prepared according to Examples 1 and/or 12 of British Patent No. 880,897. St-andapon is a nonyl phenol ether of polyethylene glycol containing 10 to 10.5 ethylene oxide units.

Example 2 The following dye bath was prepared:

Nylon yarn, similar to that used in the first example, was taken directly from the pim, led through the dyestuff solution, and onto the heater element of a Superloft bulking machine as shown in FIGURE 1 and wound on a bulking spindle. The yarn was processed at 440 F. over a 9" Superloft block. at 42% yards per minute. There was little or no smoking or fu-ming, of the yarn while passing over the Superloft heating block and no odor was noted in the finished yarn. The yarn was processed similarly as in Example 1 and had the same characteristics.

Example 3 Nylon yarn was dyed by passing the same through a dye bath containing Blue (permanent tint): Percent Celanthrene blue FFS 3.29 Water 80.61 Stanax 15.00 Sodium bicarbonate 1.00 Standapon 0.10

at a roll speed of 8 r.p.m., the yarn traveling at a speed of approximately 700 yards per minute. After dyeing, the yarn was wound on a spindle and dried for 30 minutes at 225 F. Thereafter, the conditioned yarn was processed through a Whitin-A.R.C.T. stretch machine while being converted into 2-ply in the operation. The yarn was processed at 425 F. over a 22" heater. The resulting bulked yarn was processed as indicated in Example 1. The results were similar.

Example 4 Comparative results of yarns processed in the presence of, and in the absence of, an antistatic agent A nylon yarn (70-34-AZ-RSD) was processed by passing the same through one of the following dye baths:

. 9 Dye bath 3: Percent Irgalan red 4GL 1.00 Standapon 0.20 Water 98.80

The dyestuif solution was applied from a coning trough of a winding machine using a roll speed of from to 15 rpm. in order to obtain approximately 20% pick-up of the dyestuff solution on the yarn. The yarn was taken up on a cone and placed in a steam chamber and steamed at atmospheric pressure to slightly elevated pressures for a period of 30 minutes. Thereafter, the yarn was dried in an over at a temperature of 225 F. The purpose of the steaming operation was to insure more uniform penetration of the dyestutf into the yarn. The three sets of conditioned yarn from dye baths 1, 2 and 3 above were proc-' essed through a Fluflon stretch machine with radiant heat and converted to ,2-ply in the operation. The sets of yarn from dye baths 1 and 2 processed satisfactorily though the false-twist machine. While the set of yarn from dye bath 3 could be processed on this equipment, it was very abrasive and the frictional drag was very high.

The bulked product from the sets of yarn from dye baths 1, 2 and 3 was knitted and tested as in Example 1.

All three sets processed without difficulty and had excellent properties as to color fastnes's. The non-permanent antistatic agent utilized in dye-bath 2, Stantex 1032, a clear, pale, water-emulsifiable oil having a composition of about 66% parts white mineral oil, 18% parts degraded triglyceride, 5 parts potassium soap of a higher fatty acid, and parts of a sulfated fatty ester, was not as effective in antistatic properties after five domestic launderings as was the permanent antistatic agent used in dye bath 1.

Example 5 Comparative results of yarns processed in the presence of, and in the absence of, an antistatic agent The dyestulf solution was applied from'a coning trough of a winding machine using a roll speed of from 5 to rpm. inorder to obtain approximately pick-up of the dyestutf solution on the yarn. The yarn was taken up on a cone and placed in a steam chamber and steamed at atmospheric pressure to slightly elevated pressures for a period of 30 minutes. Thereafter the yarn was dried in an oven at a temperature of 225 F. The purpose of the steaming operaiton was to insure more uniform penetration of the dyestutf into the yarn. The three sets of conditioned yarn from dye baths 1, 2 and 3 above were A nylon yarn (-34- /2 Z-RSD) was processed by passing the same through one of the following dye baths:

Dye bath 1: v Percent lrgalan brilliant green 3 1.00 Stanax 7.50 Standapon 0.10 Sodium bicarbonate 2.00 Water 89.40

- Dye bath 2: I Percent Irgalan brilliant green 3 1.00

Stantex 1032 7.50 Standapon 0.20 Water 91.39

Dye bath 3: t Percent llrgalan brilliant green 3 1.00 Standapon 0.20 Water 98.80

cording to FIG. 3 with "radiant heat and converted to 2-ply in the operation. The three sets of yarn were either processed over a 9" Superloft block under identical conditions of heat and speed of travel or through a radiant heat chamber of the Fluflon machine. The sets of yarn from dye baths 1 and 2 processed satisfactorily through the Superloft false-twist machine, but the set of yarn from dye bath 3 could not be made to run at all on this equipment. This yarn was very abrasive and the frictional drag was very high.

The bulked product from the sets of yarn. from dye baths 1 and 2 which was processed through the Superloft machine, was knitted and tested as in Example 1. Both sets processed without diflieulty and had excellent properties as to color fastness.

The sets of yarn processed through the Fluflon machine gave similar results as in Example 4. The sets of yarn Comparative results of yarns processed'with' high-temperature-stable antistatic agents A nylon yarn (70-34-lZ-RSD) was processed by passing the same through one of the following dye baths contained in the coning trough of a No. 50 Universal" winder. The roll speed and percent solution pickup for each cone is also noted. After dyeing, the cones were steamed for 30 minutes followed by drying for minutes at 225 F., then lagged overnight and retubed.

Dye bath 1: Percent Irgalan red 4GL 1.00 Stantex 1032 7.50 Standapon 0.20 Water 91.30

8.5 r.p.m., 18.3% solution pickup.

Dye bath 2: Percent Irgalan red 4GL 1.00 Stantex 201A 7.50 Standapon 0.20 Water 91.30

10 r.p.m., 23.7% solution pickup.

Dye bath 3: Percent Irgalan red 46L 1.00 Stantex P 7.50 Standapon 0.20 Water 91.30

9.5 r.p.m., 20.8% solution pickup.

Dye bath 4: Percent Irgalan red 4GL 1.00 Standapon 0.20 Water 98.80

14% r.p.m., 19.0% solution pickup.

Dye bath 5 Percent Du Ponts oil red powder 2.00 Stantex 110D 15.00 Varsol 83.00

24 rpm, 11.8 solution pickup.

Dye bath 6: Percent Irgalan brilliant green 3GL 1.00 Stantex 1032 7.50 Standapon 0.20 Water 91.30

r.p.m., 19.0% Solution pickup.

Dye bath 7: Percent i Irgal-an brilliant green 3GL 1.00 Stantex 201A 7.50 Standapon 0.20 Water 91.30

10 r.p.m., 21.4% solution pickup.

Dye bath 8: Percent Irgalan brilliant green 3GL 1.00 Stantex llOP 7.50 Standapon 0.20 Water 91.30

12 r.p.m., 23.8% solution pickup.

Dye bath 9: Percent Irgalan brilliant green 36L 1.00 Standapon 0.20 Water 98.80

14% r.p.m., 20.4% solution pickup.

Dye bath 10: Percent Du Ponts oil blue A powder 0.5 Du Ponts oil yellow powder 1.5 Stantex 110D 15.0 Varsol 83.0

24 r.p.m., 12.2% solution pickup.

The ten cones of yarn processed satisfactorily through the Fulflon machine with the following results.

Tension above Dye Bath No. Antlstutic Agent Spindle Smoke or ol the Fumes Fluilon machine, grams 1. Btantex 1032 18 Excessive. 2. Stnntex 201A 13 Medium. 3. Stantex 1101 12 Light. 4. None 20 Do. 5. Stantex 110 12 Do. 0. Stantex 1032... Excessive 7. Stunt-ex 201A 15 Light. 8. Stantex 110P 15 Do 9. N one 22 Do. Stantex 110D-. 15 Medium.

The presence of a lubricant/antistatic agent was made evident by the lower tensions above the spindle as compared to the formulations without the antistatic agents.

It can be also noted that the conventional antistatic agents as exemplified by Stantex 1032 gave excessive smoking or fuming as compared to the high-temperature-stable antistatic agents.

Stantex 1032 is a clear, pale, water-emulsifiable oil having a composition of about 66% parts white mineral oil, 18 /3 parts degraded triglyceride, 5 parts potassium soap of a higher fatty acid, and 10 parts of a sulfated fatty ester.

Stantex 110D corresponds to the product of Example 1 of Ser. No. 269,186 and is an ester of the formula /Cu n I l(C:H:,OII)gNlIg]*[CuHnH-C000C:

CflI This ester is compounded with about an equal weight of hexadecyl stearate and a small amount of a bactericidc.

Stantex 201A corresponds to the product Stantex D, further compounded with a polyethylene glycol 400 monolaurate to make the composition water-emulsifiable.

Stantex 110P is a water and solvent soluble material prepared according to Ser. No. 346,390. It is a reaction product formed by esterifying alpha-sulfopalmitic acid with an ethoxylated alcohol, a mixture of C1648 alkanols condensed with an average of 8.85 moles of ethylene oxide. This is done in the same manner as outlined in the examples of Ser. No. 346,390, that is, the reaction is carried out in a solvent medium (naphtha). After esterification, the sulfonic acid group is neutralized with diethanolamine and the solvent removed by distillation. The thus prepared ester-salt is then compounded with hexadecyl stearate in the following manner:

- Percent Finished 110P ester 49.875

'' Hexadecyl stearate 49.875

Dowicide No. 1 0.250

smoke point, (2) volatility at 221F., and (3) volatility at 392 F. (percent loss after 4 hours).

Htantcx Stnntox Stnntex Stantox 1032 110i) 110i Z0111v Smoke Point, 1" H 1.54 21! 240 285 Volntillty at 221 1'. (percent). b. 4 4.1 2.0 Volatlllty at 302 F. (percent loss after 4 hrs.) 30. 70 ll. 07 10. 32 22. 00

1 Keeps volntliizlng indefinitely.

Example 7 Comparative results of yarns processed with a simultaneous dyeing and bulking operation Nylon yarn (70-17-VzZ-LOS) was processed through a modified Superloft machine. The equipment was modified to permit the yarn as it is taken off the producer's pirn to be dyed and texturized in one operation. The yarn is wrapped around a grooved roller which permits the yarn to make from l-6 passes through the dye bath trough followed by immediate bulking, all in one operation. The yarn, after passing through the dye bath was run on a modified Superloft machine using a 28" heater block, run at 45 yards per minute with 83 turns per inch inserted at Dye bath 1:

13 a temperature of 420 F. All solutions were run using the same conditions.

The following dye bath formulations were applied:

Percent Irgalan red 4GL -2 1.00 Stantex 1032 a 7.50 Standapon 0.20 Water 91.30

8.5 r.p.m., 18.3% solution pickup.

Dye bath 2: 2 Percent -Irgalan red 4GL -2. 1.00 Stantex 201A 7.50 Standapon -2 0.20 Water 91.30

10 r.p.m., 23.7% solution pickup.

Dye bath 3: Percent Irgalan red 4GL 1.00 Stantex 110P 7.50 Standapon 0.20 Water 91.30

9.5 r.p.m., 20.8% solution pickup.

Dye bath 4: Percent Irgalan red 4GL 1.00 Standapon 0.20 Water 98.80

14% r.p.m., 19.0% solution pickup.

Dye bath 5: Percent Irgalan brilliant green 36L 1.00 Stantex 103 2 7.50 Standapon 0.20

- Water 91.30

'10 r.p.m., 19.0% solution pickup.

Dye bath 6: Percent lrgalan brilliant green 30L 1.00 Stantex 201A 7.50 Standapon 0.20 Water 91.30

10 r.p.m., 21.4% solution pickup.

Dye bath 7: Percent Irgalan brilliant green 3GL 1.00 Stantex llOP 7.50 Standapon 0.20 Water 91.30

12 r.p.m., 23.8% solution pickup.

Dye bath-8: Percent Ir-galan brillant green 36L 1.00 Standapon 0.20 Water 98.80

14% r.p.m., 20.4% solution pickup.

14 Dye bath 9: Percent -Dn Ponts oil blue A powder 0.5 Du Ponts oil yellow powder 1.5 Stantex 110D 15.0 Varsol 83.0

m sasses e 24 r.p.m., 12.2% solution pickup.

Under the circumstances of this process, wherein the moist yarn was run in contact with the Superloft heater.

block, even the yarns from dye baths 4 and 8, containing no antistatic agent could be processed, as compared with Example 5. However the yarn from dye baths 4 and 8 processed with difficulty as compared with the rest of the yarns, with excessive breakage. It was impossible to utilize the equipment without constant attention. The following results were observed.

Smoke or Fumes Excessive. Ltg

. None Stantox 110D The texturized dyed ya'rn w-as'then knit into tubes and Comparative results of yarns processed at lower concentrations of antistatic agents Non-fuming nylon yarn (-17-%Z-LOS) was processed by passing the same through a dyebath in a coning trough of a sizing machine. The roll speed was 10 r.p.m. and the spindle sizing tube speed was 1450-1470 r.p.m. Approximately 37% of the dye bath formulation was applied to the yarn, after which the dyed yarn was dried in an oven set at a 130 F. dry bulb temperature and 125 F. wet bulb temperature for 30 minutes. After lagging overnight the yarn was bulked using conventional texturizin'g equipment such as a 553 Superloft machine having a heater block 36 inches in length, the temperature of the heater block was 460 F., the spindle speed was 238,000 r.p.m. and turns were'imparted to a 1 inch of 'yarn, followed by plying and knitting into a representative tubing (or sleeve).

The following dye baths were employed:

The four cones of dyed yarn bulked very satisfactorily and the following physical test results were reported as being representative of a very good bulked yarn.

Cone A Gone 11 Cone Cone 1) Percent Relaxation 01.1 61.1 62.0 61.1 Breaking Strength rgrnms/ denier) 3. 39 3. 18 3. 07 3. M

The dyed texturized physical properties.

The preceding specific embodiments of the invention enable one skilled in the art to better comprehend the same. It is to be understood that changes and modifications can be made therein without departing from the spirit of the invention and the scope of the appended claims.

We claim:

1. The process of bulking dyed thermoplastic yarn which comprises the steps of incorporating on said dyed thermoplastic yarn from about 0.1% to about 8% of an high-temperature-stable, antistatic agent, continually twisting the dyed thermoplastic yarn containing said antistatic agent incorporated thereon, continually passing the yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat the yarn to a prescribed temperature to reorient the molecules of the yarn to the twisted formation of the yarn and yarn-set the same, continually cooling the yarn to. stabilize the same, continually untwisting the yarn after cooling the same, and continually collecting the evenly and substantially permanently crimped, wavy or fluffed dyed thermoplastic yarn having from about0.1% to about 8% of said antistatic agent incorporated thereon.

2. The process of bulking dyed thermoplastic yarn which comprises the steps of incorporating on said dyed thermoplastic yarn from about 0.1% to about 8% of a water-soluble resinous hardenable condensation product containing cpoxide and halogen groups as an antistatic agent, continually twisting the dyed thermoplastic yarn containing said antistatic agent incorporated thereon, continually passing the yarn at a selected linear speed under yarns, when knitted, had excellent uniform tension through a restricted thermally isolated heated zone to uniformly heat the yarn to a prescribed temperature to reorient the molecules of the yarn to the twisted formation of the yarn and yarn-set the same, continually cooling the yarn to stabilize the same, continually untwisting the yarn after cooling the same, and continually collecting the evenly and substantially permanently crimped, wavy or fiuffed dyed thermoplastic yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon.

3. The process of bulking dyed thermoplastic yarn which comprises the steps of incorporating on said dyed thermoplastic yarn from about 0.1% to about 8% of a composition containing mineral oil, partially saponified triglycerides and sulfated fatty esters as an antistatic agent, continually twisting the dyed thermoplastic yarn containing said antistatic agent incorporated thereon, continually passing the yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat the yarn to a prescribed temperature to reorient the molecules of the yarn to the twisted formation of the yarn and yarn-set the same, continually cooling the yarn to stabilize the same, continually untwisting the yarn after cooling the same, and continually collecting the evenly and substantially permanently crimped, wavy or tluffed dyed thermoplastic yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon.

4. The ,process of bulking dyed thermoplastic yarn which comprises the steps of incorporating on said dyed thermoplastic yarn from about 0.1% to about 8% of a high-temperature-stable organic amine salt of an ester of an alphasulfo higher fatty acid antistatic agent, continually twisting the dyed thermoplastic yarn containing said antistatic agent incorporated thereon, continually passing the yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat the yarn to a temperature in excess of 400 F. to reorient the molecules of the yarn to the twisted formation of the yarn and yarn-set the same, continually cooling the yarn to stabilize the same, continually untwisting the yarn after cooling the same, and continually collecting the evenly and substantially permanently crimped, wavy or fluffed dyed thermoplastic yarn having from'about 0.1% to about 8% of said antistatic agent incorporated thereon.

5. A method of fastly and uniformly dyeing while producing evenly and substantially permanently crimped, wavy or fiuffed multi-filament yarn capable of undergoing thermoplastic deformation, said yarn having improved and uniform physical characteristics, which comprises the steps of continually drawing the yarn from a source of supply, continually applying a dye 'bath containing from about 2% to about 20% of a compatible, high-temperature-stable, antistatic agent to the traveling yarn, continually twisting said dyed yarn containing said antistatic agent incorporated thereon, continually passing said twisted yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat said yarn to a prescribed temperature to dry and develop the dyestulf and reorient the molecules of said yarn to the twisted formation of the yarn and yarn-set the same, continually cooling said yarn to stabilize the same, continually untwisting said yarn after cooling the same, and continually collecting said bulked dyed yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon. l

6. The process of claim 5 wherein from about 0.3% to about 5%, based on the weight of said dyed, texturizcd yarn, of an antistatic agent is incorporated thereon.

7. A method of fastly and uniformly dyeing while producing evenly and substantially permanently crimped, wavy or fluffed multi-filament thermoplastic yarn, said yarn having improved and uniform physical characteristics, which comprises the steps of continually drawing the yarn from a source of supply, continually applying a dye bath containing from about 2% to about 20% of a compatible, high-temperature-stable, antistatic agent to the traveling yarn, continually twisting said dyed yarn containing said antistatic agent incorporated thereon, continually passing said twisted yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat said yarn to a prescribed temperature to dry and develop the dyestulf andreorient the molecules of said yarn to the twisted formation of the yarn and yarn-set the same, continually cooling said yarn to stabilize the same, continually untwisting said yarn after cooling the same, and continually collecting saidtexturized dyed yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon.

8. A method of fastly and uniformly dyeing while producing evenly and substantially permanently crimped, wavy or fluffed multi-filament yarn coated with thermoplastic resin, said yarn having improved and uniform physical characteristics, which comprises the steps of continually drawing the dyed yarn from a source of supply, continually applying from about 011% to about 8% of an high-temperaturc-stable, antistatic agent based on the weight of the yarn to the traveling yarn, continually twisting said dyed yarn containing said antistatic agent 17 incorporated thereon, continually passing said twisted yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat said yarn to a prescribed temperature to reorient the molecules of said yarn to the twisted formation of the yarn and yarn-set the same continually cooling said yarn to stabilize the same, continually untwisting said yarn after cooling the same, and continually collecting said tenturized dyedyarn having from about 0.1% to about t3% of said antistatic agent incorporated thereon. 9. A method of fastly and uniformly dyeing while producing evenly and substantially permanently crimped, wavy or flulfed multi-filament thermoplastic yarn, said yarn having improved and uniform physical characteristics, which comprises the steps of continually drawing the yarn from a source of supply, continually applying an aqueous dye bath containing a water-soluble resinous hardenable condensation product containing epoxide and halogen groups as an antistatic agent, wherein from about 0.1% to about 8%, 'based on the weight of said yarn, of said antistatic agent is incorporated thereon, to the traveling yarn, continually twisting said dyed yarn conheated zone to uniformly'heat said yarn to a prescribed taining an antistatic agent incorporated thereon, continually passing said twisted yarn at'a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat said yarn to a prescribed temperature to dry and develop the dyestuif and said antistatic agent and reorient the molecules of said yarn to the twisted formation of the yarn and yarnset the same, continually cooling said yarn tostabilize the same, continually untwisting said yarn after cooling the same, and continually collecting said texturized dyed yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon. Y

10. A method of 'fastly and uniformly dyeing while producing evenly and substantially permanently crimped, wavy or fluffed multi-filament thermoplastic yarn, said yarn having improved and uniform physical characteristics, which comprises the steps of continually drawing the yarn from a source of supply, continually applying an aqueous dye bath containing a composition containing,

mineral oil, partially saponifiedtriglycerides and sulfated fatty esters as an antistatic agent, wherein from about 0.1% to about 8%, based on the weight ofsaid yarn, of said antistatic agent is incorpoarted thereon, to the traveling yarn, continually twisting said dyed yarn containing an antistatic agent incorporated thereon, continually passing said twisted yarn at a selected linear speed under temperature to dry and develop the dyestuif and reorient the molecules of said yarn to the twisted formation of the yarn and yarn-set the same, continually cooling said yarn to stabilize the same, continually untwisting said yarn after cooling the same, and continually collecting said texturized dyed yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon, based on the weight of said texturized, dyed yarn. 1

11. A method of fastly and uniformly dyeing while producing evenly and substantially permanently crimped, wavy or tluiied multi-filament thermoplastic yarn, said yarn having improved and uniform physical characteristics, which comprises the steps of continually drawing the yarn from a source of supply, continually applying a dye bath containing a high-temperature-stable organic amine salt of an ester of an alphasulfo higher fatty acid as an antistatic agent, wherein from about 0.1% to about 8%, based on the weight of said yarn, of said antistatic agent is incorporated thereon, to the traveling yarn, continually twisting said dyed yarn containing said antistatic agent incorporated thereon, continually passing said twisted yarn at a selected linear speed under uniform tension through a restricted thermally isolated heated zone to uniformly heat said yarn to a temperature-in excess of 400 F. to dry and develop the dyestuif and to reorient the molecules of said yarn to the twisted formation of the yarn andyarn-set the same, continually cooling said yarn to stabilize the same, continually untwisting said yarn after cooling the same, and continually collecting said texturized dyed yarn having from about 0.1% to about 8% of said antistatic agent incorporated thereon.

References Cited by the Examiner UNITED STATES PATENTS 2,150,570 3/1939 Whitehead 12-46 x 2,298,432 10/1942 Thompson. 2,803,109 8/1957 Stoddard-ct al. 57-157 3,077,724 2/1963 Stoddard et al. s7--34 3,108,011 10/1963 Frotscher 8-18X FOREIGN PATENTS 380,042 8/1932 Great Britain.

MERVIN STEIN, Primary Examiner. 

2. THE PROCESS OF BULKING DYED THERMOPLASTIC YARB WHICH COMPRISES THE STEPS OF INCORPORATING ON SAID DYED THERMOPLASTIC YARN FORM ABOUT 0.1% TO ABOUT 8% OF A WATER-SOLUBLE RESINOUS HARDENABLE CONDENSATION PRODUCT CONTAINING EXPOXIDE AND HALOGEN GROUPS AS AN ANTISTATIC AGENT, CONTINUALLY TWISTING THE DYED THERMOPLASTIC YARN CONTAINING SAID ANTISTATIC AGENT INCORPORATED THEREON, CONTINUALLY PASSING THE YARN AT A SELECTED LINEAR SPEED UNDER UNIFORM TENSION THROUGH A RESTRICTED THERMALLY ISOLATED HEATED ZONE TO UNIFORMLY HEAT THE YARN TO A PRESCRIBED TEMPERATURE TO REORIENT THE MOLECULES OF THE YARN TO THE TWISTED FORMATION OF THE YARN AND YARN-SET THE SAME, CONTINUALLY COOLING THE YARN TO STABILIZE THE SAME, CONTINUALLY UNTWISTING THE YARN AFTER COOLING THE SAME, AND CONTINUALLY COLLECTING THE EVENLY AND SUBSTANTIALLY PERMANENTLY CRIMPED, WAVY OR FLUFFED DYED THERMOPLASTIC YARN HAVING FROM ABOUT 0.1% TO ABOUT 8% OF SAID ANTISTATIC AGENT INCORPORATED THEREON. 